DE2365265A1 - MOLECULARSIES AND THEIR PRODUCTION - Google Patents

Description

PATENT LAWYERS _{Ä A}

Dipl.-Ing. P. WIRTH Dr. V. SCHMIED-KOWARZIK Dipl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 β FRANKFURT AM MAIN

TELEPHONE C0611)

287014 GR. ESCHENHEIMER STRASSE 39

MffP-616 Toyo Wd / Sch

TOYO JOZO COMPANY, LTD.

632r-1, Ohohitocho Mifuku

Tagata gun

Shizuoka

Japan

Molecular sieve and its manufacture .

409828/0860

The present invention relates to novel molecular sieve particles and to a process for their production; in particular, it relates to molecular sieve particles containing adsorbents which are present in the bulk of "ladder"

polymer gels are dispersed.

Heretofore, adsorbents, particularly activated carbon, have been known for their excellent adsorbability. To improve the adsorption capacity of activated carbon, the surface area per unit weight is increased. Therefore, activated carbon is usually used in the form of very fine powders. However, this causes inconvenience in handling because fine powders are easily blown up and also tend to clog filter devices when the activated carbon is removed after use. In order to eliminate these disadvantages of fine powders, the use of activated carbon in the form of Granules suggested. Various methods of producing activated carbon granules are known, and several types of activated carbon granules are commercially available. Some of these activated carbon granules are known to have a molecular sieving effect, although their effectiveness is lower compared to finely powdered activated carbon. So zei "gen example carbonated products produced by pyrolysis (at 800-1200 ⁰ C) were obtained from activated carbon with polymers such as vinylidene chloride-vinyl chloride Mischpolymer'isat (Saran) or vinyl Chloridpolymerisat, a molecular sieve (Emmett, PH, Chem . Ref. 43, 69, 1948). The molecular sieve effect of these activated carbon granules is such that it is only effective in low molecular weight compounds with a molecular weight of at most 150 and a molecular size between 4 and 6 2 . Therefore they can only be used for the separation of gaseous components in petrochemicals. In addition, the molecular sieve effect of the known activated carbon granules is insufficient to bring about complete sieve separation. You can therefore not be used to separate or purify antibiotics, pigments, nucleic acids, proteins,

* "ladder"

409828/0860

Enzymes and the like or for the treatment of consumed Liquids from which the organic compounds are to be removed can be used.

The object of the present invention is to provide novel molecular sieve particles which are excellent in molecular sieving action and have excellent adsorption capacity, as well as the creation of a method of manufacture of these molecular sieve particles.

The present invention relates to molecular sieve particles which are characterized as being adsorbents which are dispersed in the matrix of polymeric gels.

According to the invention, powder of activated carbon, aluminum oxide, silica gel, celite, bentonite, ion exchange resin, Calcium phosphate gel and chelate resin can be used. Any other adsorbent can be used as long as it has an adsorptive capacity.

The Malekularsiebmittel invention has a special structure, _W dispersed obei the Adsorptionspulver in the matrix of the Leiterpolymerisatgele. The molecular sieve effect of the molecular sieve particles of the present invention is ascribed to this structure. Micropores, which are present in the entire matrix, act as a sieve, in other words, they let through a substance which has a smaller molecular size than the size of the micropores, allowing sufficient contact with the adsorbent powders dispersed in the matrix, while they do not let through a substance which has a larger molecular size than the size of the micropores in the matrix and thereby prevent such a substance from coming into contact with the adsorbent powders. Therefore, both the size of the pores and the uniformity of the pores are important for effective molecular sieving. It has been found that the conductor used according to the invention

409828/0860

polymer gels a suitable substrate for creating such Form micropores,

The invention also provides a process for the preparation of o "is ben mentioned molecular sieve created He invention sgemäße retracts, comprising the steps of dispersing ι is dissolved the Adsorptionspulver in a solution of polymeric material in a solvent 5 then dispersing the resulting dispersion in a Hilfsmed.i «IB. (" Vehicle ") with a boiling point; which is higher than that of the solventS _{9 in} order to form fine {droplets ^ and finally remove the solvent"

G-emäß a preferred embodiment of the method according to the invention, a solvent is _5, the yesentlichen i-in with water immiscible and a lower boiling point nnä higher vapor pressure than water ₉ has a polymeric material which is soluble in said solvent _S and a cosolvent ₉ consisting of an aqueous solution of a surfactant or a hydrophilic protective colloid is ₉ is used (method a) ₀ G-emäß a further preferred embodiment of the present invention xvird an organic solvent = Medium ;, essentially = with liquid paraffin or silicone oil is not miscible, but is miscible with water and has a lower boiling point and higher vapor pressure than water, when mixed with water5 a polymeric material; which is soluble in this solvent5 and an auxiliary medium of liquid paraffin or silicone oil is used (method B) ₀ Both methods are used described in detail below?

I ₀ Procedure A

The solvents that are essentially immiscible with water are solvents that are either completely water-soluble immiscible or miscible with a maximum of $ 15 water »you should have a lower boiling point and higher vapor pressure

28 /

as water. There are tons of, for example, _{ethyl ether 9} isopropyl ether, methylene chloride, ethylene chloride _? Chloroform, carbon tetrachloride, benzene, cyclohexane, n-hexane or ₉ Metliylacetat Äthylaoetat used. These solvents can either be used alone or mixed.

As a polymeric material which is soluble in the above solvents _s of each polymer can be used which does not deactivated the AdsorptionspulVer "■ It can, for example, ethyl cellulose, cellulose acetate, hydroxypropylmethylcellulose phthalate, polyvinyl formal, polyvinyl butyral, Polyvinylacetaldiäthylaminoacetatj polyester polystyrene, Yinylchlorid-Yinylacetat-Mischpolyraerisat ₉ Yinylchlorid -Yinyl propionate mixed polymer and phenylsiloxane ladder polymer used v / earth. Ethyl _{cellulose s} ■ Cellulose acetate and polyvinyl formal are "particularly" preferred due to their water permeability and mechanical strength «,

As an auxiliary solution is an aqueous solution of a surfactant or a hydrophilic protective colloid is used which are powder dispersed in the polymer solution, the droplets of the dispersion in which the adsorption s-, are "stable and not deactivated this Adsorptionspulver. An aqueous solution of a surfactant which is suitable for use, contains about 0.01 to 5 $ _s preferably about 0.25 to 2 #, of an anionic surface active agent, such as _s beispielsiireise alkylbenzenesulfonates Hewlex R / lex ₉ Mev C-1 or Uewlex paste H, sulfonated Alkyl esters of organic two-T base acids, such as lapizol B, and sodium salts of sulfuric acid esters of higher alcohols, such as Syntolex , Methyl cellulose, hydroxypropylmethyl cellulose, or polyvinyl alcohol, these surfactants and hydrophilic protective colloids can also be combined

409828/0860

■ = ■ β = - uses v / earth ₀

When this process is carried out, the polymer. Material first dissolved in the solvent, the concentration of the polymeric material can vary and depends on the used polymeric material or the solvent used from ₀ if the concentration to ho eh IBt ₉ is the dispersion ability is adsorbent bad "If the concentration dagegen- zn low, the droplets formed in the auxiliary solution are not "stable, and the removal of the solvent takes a long time. The concentration" is therefore generally about O ₅ 5 = 20 fo _9, preferably about 2 = 10 fa ₀ Ia the solvent or the solution of polymeric material I can also use suspension _{powder 9} such as talc _? Silicon starch, titanium dioxide, l ^ agnesiutakarbonat "or" aluminum =

added x-zerdenj to form _{permanent droplets 9} the poles are dispersed in the auxiliary solution

In the next stage, the adsorbent powder is dispersed in the polymeric material. The amount of adsorbent powder is ia 5%. or more _s, preferably about 40 = 85 .. ^ of the molecular life particles obtained. This dispersion is "dispersed in the auxiliary solution and" forms fine "droplets. H @ age the polymer © _ nlösisng used _a Di @ Hührbedingungen for producing the fine droplets in DER .Dispersion depend on the used polymeric material _s of the concentration of droplets in the dispergisrten "contains @ n © n poljaeren material _P meag © to Adsorptionsmittsl _s the amount aa Help slö awig and, -the 5? @ il © h @ ngröß @ Aeee final product from _o Finally Lieh IABT you die! dispersion are in the form of feiaea droplets Rüteen "bsi room = temperature _p then si is © heated or ä r & pressure ver = Binäertp to the solvent to be entfera. @ ₉ wherein n = dia polymer seis ₉ the Adsorptionspulver be precipitated enthaltest dl © Molekularsiebteilehen invention form the ^. collected _s . be washed and dried _o

365265

Procedure B

The solvents which "can be used in mixture with water in this process ₉ are essentially not miscible with liquid paraffin or sillkon oil, which is used as an auxiliary medium; however, they are" miscible with water and have a lower boiling point and higher vapor pressure ο than water examples of these solvents are acetone, methyl ethyl ketone, methanol, ethanol and propanols of these, v / ground acetone and methanol preferably _s as they can easily dissolve the polymeric materials listed below _9, and since they also have a mixture with water * a boiling point xvird which is far below that of water. the water content in the solvent may be in the range ₉ in which still no precipitation of the polymeric material caused ₉ Vorzugsv / else on the upper limit of this BereiehSo the appropriate amount of water with the The solvent used depends on the combination of the solvent used and the • polymer en material and its concentration from _o If the concentration of the polymeric material in the appropriate range, z »B _o between about 5 and 1Θ wt./Vol.-#, is a water content between about 2 Volo / Volo- ^ and 20 vol./vol

desirable »¥ orz" gseise Iceton is a 'content τοη about 7-15 Vol./VoI.-$6 water and methanol containing ■ • won about 3-10 Vol./VoI,-Ji water used, when the concentration of polymer material is low _? the amount of water can be increased. On the other hand, if the concentration of rem material is high, the amount of water can be reduced

The amount of water can also vary depending on the conditions be adjusted.

The polymeric material used in this process can »is in the above organic solvents Easily soluble, preferably in hydrous organic solvents. Examples of polymeric material that can be used are cellulose acetate, cellulose acetate phthalate, cellulose acetate butylaminohydroxypropyl ether, Hydroxypropyl methyl cellulose

40982 8/0860

phthalate, cellulose butyrate, cellulose propionate, ethyl cellulose, Hydroxypropylmethylcellulose trimellitate, yinyl chloride-yinyl propionate copolymer, Yinylacetate-yinyl chloride copolymer , Polyvinylaeetaldiethylaminoacetat, styrene-maleic acid-ethylene miseh polymer, Ethylene-yinylacetate-copolymer and acrylic acid-methacrylic acid-copolymer'o These polymers te are dissolved in the solvents mentioned above. The concentration of the polymeric material is suitably limited between about 5 and 10 wt / vol%, from the same Reasons given for procedure A. Thereafter, an appropriate amount of water as described above is added to the solution given. However, the polymeric material can also be dissolved directly in a water-containing organic solvent.

Then adsorbent powders are dispersed in the polymeric solution, preferably in amounts between about 50 and 80 w / w based on the produced molecular sieve particles. If the amount is too small, the adsorption capacity is per volume weight of the molecular sieve particles too bad. On the other hand, if the amount is too high, the molecular sieve particles are too brittle. _ - '

Liquid paraffins, such as flowable paraffins, paraffins from the Japanese Pharmacopeia "or halogen-containing paraffins or silicone oils, such as methyl silicone oil, phenyl silicone oil or methylphenyl silicone oil, can be used as auxiliary media. These auxiliary media have a high viscosity and are of an inert nature. The above-mentioned organic solvent solution, wherein the Adsorptionspulver are dispersed is dispersed with stirring in emulsions. suspension stabilizing agent that does not deactivate the adsorption ability of the adsorbent can be added to obtain a favorable dispersion. the amount of auxiliary smedium is preferably about 4 -.15 times the Amount of the organic solvent solution: If the amount is too small, the emulsified droplets adhere to each other and form agglomerates, but if the amount is too large, the extraction of the molecular sieve particles is complicated

409828/0860

2365285

- 9 procedures described under A.

Molecular sieve particles approximately 0.3-2.0 mm in size can be obtained by either of the two methods described above produce which have an excellent molecular sieve effect and a high adsorption capacity. In both procedures the combination of the solvents, the polymeric material and the auxiliary medium is critical for the formation of the micropores in the Base mass of the polymer gel.

It has been found that the molecular sieve particles of the present invention have a unique molecular sieve effect. That is, the molecular sieve particles are capable of organic compounds to adsorb selectively according to their molecular weight. The size range of micropores formed in the matrix estimated at around £ 8-40. Therefore, with the invention Molecular sieve particles - in contrast to the previously known molecular sieve particles - also a selective adsor. Beer of organic high molecular weight compounds possible. In addition, according to the method according to the invention different molecular sieve particles having different molecular sieve effects can be easily produced. So amounts in one example, the molecular weight of the organic adsorptive compound is 1,280 or less and the molecular weight of the non-adsorptive organic compound 5,700 or more, while in another example the molecular weight of adsorptive organic compound 10,000 or less and the molecular weight of the non-adsorptive organic compound 22,000 or more. . *

The molecular sieve particles of the invention can be used for many various purposes can be used by taking advantage of the above-mentioned unique molecular sieving effect and excellent adsorbing ability. Examples include direct collecting different fermented products from different growth fluids, the separation of antibiotics absorbed in the serum, the cleaning of raw organic compounds, that

409828/0860

- ίο -.

effective collection of useful organic compounds from natural productsj the recovery of useful organic compounds from used liquids with simultaneous discoloration of these used liquids and so on.

The following examples serve to explain the present invention in more detail.

example 1

Various molecular sieve particles containing adsorbents are prepared by the method-A of the present invention using the following ingredients. For each sample, a wall material is first dissolved in a solvent. Activated carbon is dispersed in this solution. The dispersion is added at room temperature with stirring to an aqueous solution in which a surface-active agent or a hydrophilic protective colloid is dissolved. Stirring is continued until the solvent has evaporated and particles form, the adsorbent gelling in solid semipermeable membranes. Polymerizaten is included »The particles are separated by filtration and then washed several times with water and ^{dried at 40 °} C. in a stream of air, and molecular sieve particles with a molecular sieve effect are obtained.

(a) Adsorbent: Kyoryoku Shirasagi (brand name,

Product of Takeda Chemical Industries), 90 g

"Wall polymer"? Ithyl cellulose (50 cP), 30 g Solvent? Methylene chloride, 1200 ml auxiliary medium: aqueous solution of 30 g sodium

Laurylbenzenesulfonate, 6000 ml product? 112 g _f size from about 0.25 - 1.5 mm.

409823/0860

("b) Adsorbent:" Wall polymer ": Solvent: auxiliary medium:

Product:

(c) Adsorbent: "Wall polymer ^u : Solvent: Auxiliary medium:

Product:

(d) Adsorbent:

"Wall polymer":

Solvent: Auxiliary medium: _

Product:

(e) Adsorbent: "Wandpolymeri sat": Solvent: auxiliary medium:

Product:

(f) Adsorbent: "Wall polymer": Solvent: Auxiliary medium: Kyoryoku Shirasagi, 60 g cellulose acetate, 40 g methylene chloride, HOO ml aqueous solution of 30 g of sodium lauryrbenzenesulfonate, 6000 ml 114 g, size 0.25 to 1.5 mm.

Kyoryoku Shirasagi, 90 g polyvinyl formal, 30 g Methylene chloride, 1200 ml aqueous' solution of 30 g of sodium laurylbenzenesulfonate , 6000 ml 109 g, size 0.25 - 1.5 mm.

Kintsuru (brand name; activated charcoal for use "in brewing, product of Aokikogyo Co.), - 30 g vinyl chloride-vinyl acetate copolymer, 20 g
Chloroform, 700 ml aqueous solution of 0.5 # polyvinyl alcohol, 4000 ml 45 g, size-0.2-1.7 mm.

Shirasagi A (brand name), 8 g polyvinyl butyral, 2 g methylene chloride, 100 ml aqueous solution of 0.5 % sodium lauryrbenzenesulfonate, 800 ml 8 g, size 0.2-1.7 mm.

Product:

Kyoryoku Shirasagi, 60 g: ethyl cellulose (50 cP), 40 g methylene chloride, 1000 ml aqueous solution (6000 ml) of 12g hydroxypropyl cellulose (HPC, brand name, Product of Shinetsu Kagaku Co.) and 30 g of matrium lauryl / benzene sulfonate

99 g, size 0.25 - 1.5 mm. 409828/0860

Example 2

According to the method B of the present invention, various molecular sieve particles containing adsorbents are produced under the following conditions. For each preparation a "¥ andmaterial ^fl in-one is first water-containing solvent dissolved. Then, an adsorbent is dispersed homogeneously in the solution. The dispersion is then dispersed under stirring in an auxiliary medium, in order to form emulsions. The mixture is stirred until the solvent is evaporated and molecular sieve particles are obtained, the molecular sieve particles are washed, dried, and then washed and dried again.

(g) Adsorbent: "Wall polymer": Solvent: Help medium:

Conditions:

Washing and drying:

Product:

{h) adsorbent:

"WandpolymerisatV:

Solvent:

Activated charcoal (Kyoryoku Shirasagi), 225 g cellulose acetate, 150 g 13 # aqueous acetone, 350 ml Liquid paraffin (9000 ml) (product of Japanese Industrial Standard No. 4)> in which 180 g of Lanex (brand name; product of Kuroda Nippon Co.) is dissolved With an emulsion droplet size of 0.6 to 1.5 mm = 4 hours stir

repeated washing with n-hexane, then drying and subsequent Boil in 500 ml of 1N sodium hydroxide of 20 minutes, followed by washing in water and drying 380 g, size 0.6-1.5 mm.

Activated charcoal (Kyoryoku Shirasagi), 30 g

Stylite CM-2L (brand name; product.

Daido Co.), 12-20 g 10 ^ hydrous methanol, 500 ml

409828/0860

Auxiliary medium:

Stirring conditions:

Washing and drying!

Product:

(i) Adsorbent: "Wall polymer":

Solvent: auxiliary medium:

Stirring conditions:

Washing and drying: Product:

- 13 τ

Japanese Pharmacopeia liquid paraffin (1500 ml) containing 7.5 g of a surfactant (MAA-48, brand name; product of Nihon Yushi Co.) contained propeller agitation, 30Ό rpm; Size of Emulsion droplets 0.6 - 1.0 mm, stirring for 9 hours

Washed with η-hexane, dried in air and then boiled in 500 ml of an aqueous solution containing 20% alcohol for 20 minutes, then washed 3 to 4 times with water and dried, size 0.6-1.0 mm. . .

Activated charcoal (Kyoryoku Shirasagi), 6 g CABP-Wako (brand name; product of the Wako Junyaku Kogyo Co.), 4g dissolved in acetone (100 ml), then Adding water (10 ml) silicone oil (300 ml) (0-96; brand name; product of Shinetsu Kagaku Kogya Co.), wherein 1.5 g of MAA-48 are dissolved 500 rpm; Size of the emulsion droplets 0.5 to 0.8 mm, stirred for 4 hours

as in preparation (g) size 0.5 to 0.8 mm.

409828/0860

(j) Adsorbent: "Wall polymer":

Solvent:

Auxiliary medium:

Stirring conditions:

Washing and drying: Product:

(k) Adsorbent: "Wall polymer": Solvent: auxiliary medium:

Stirring conditions:

Washing and drying: Product:

- 14 -

Activated charcoal (Kyoryokü Shirasagi), 12 g

Vinyl chi or i d-Vinyla e et a t-Mis ehpolymerisat (Product of Shinetsu Zagaku Kogyo Co.), - 8 g dissolved in acetone (92 ml), then Adding water (8 ml) to liquid paraffin of the "Japanese Pharmacopeia "(800 ml), in which 8 g of squalane (brand name; product of Pa. Yamada store) are resolved

400 rpm; Size of the emulsion droplets 0.3-0.8 mm; Stirred for 6 hours

as in preparation (h) size 0.3-0.8 mm.

Activated charcoal (Kyoryoku Shirasagi), 18 g '.

Ethyl cellulose (product of Wako Junyaku Kogyo Co.), 16 g

dissolved in acetone (300 ml), followed by addition of water (30 ml)

Silicone oil (KP-96; brand name), 1200 ml, in which 6 g of MAA-48 dissolved are (brand name)

380 rpm; Stirred for 4 hours while the temperature gradually increased 45 ° C is increased

as in preparation (g) size 0.7 - 1 _t 2 mm.

409828/0860

(1) Adsorbent:

"Wall polymer":

solvent

Auxiliary medium:

Stirring conditions;
Washing and drying;

Product:
(m) adsorbent:

"Wall polymer": Solvent:
Auxiliary medium:

Stirring conditions:
Washing and drying! Product:

(n) Adsorbent: "Wall polymer": Solvent:

-15 -

Activated charcoal (Kyoryoku Shirasagi), 18 g '

Polyvinyl butyral (H ^- 4000; brand name; product of Wako Junyaku Kogyo Co.), 12 g

Methanol containing 6 # water, 150 ml

Japanese Pharmacopeia liquid paraffin (800 ml) in which 8 g Gafak LS-500 (brand name; product of Toho Kagaku Kogyo Co.) are

as in preparation (k) size 0.5 - 1.0 mm.

Amberlite CG-50 (brand name; product of Rohm & Haas Co.) powder, 6 g

Cellulose acetate, 4 g

$ 10> water-containing acetone

Japanese Pharmacopeia liquid paraffin (800 ml) in which 8 g Gafak LS-500 are solved

400 rpm

as in preparation (g)

Size 0.5 - 1.5 mm.

Amberlite CG-50 powder, 6 g ethyl cellulose ,. 4 g

10 $> Acetone containing water, 100 ml

409828/0860

Auxiliary medium:

Stirring conditions: washing and drying: product:

(o) Adsorbent:

"Wall polymer": Solvent:

Auxiliary medium:

Mixing conditions: Product:

(p) Adsorbent: "Wall polymer": Solvent:

Auxiliary medium:

Mixing conditions: Product:

- 16 -

liquid paraffin of the "Japanese Pharmacopeia ”(300 ml), in which 1.5 g of Lanex are dissolved

4 hours, stirred

as in preparation * (g) size 0.3 - 1 _f 0 mm.

Active alumina (product of Wako Junyaku Kogyo Co.), 6 g

Cellulose acetate, 4 g

Acetone containing 15 $ water, 100 ml

Silicone oil (KF-96) (300 ml) in which 3 g of Gafak LS-500 are dissolved

350 rpm

Size 0.3-0.6mm.

Amberlite CG-50 powder, 6 g Cellulose acetate, 4 g

15 $> Acetone containing water, 100 ml

liquid paraffin of the Japanese Pharmacopeia, containing 0.5 i ° Lanex

350 rpm

Size 0.3-0.6 mm.

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Comparative example

For comparison purposes, microcapsules that have no micropores are used contained in the wall layer, prepared in the same way as in Example 2, but using γρη dry Acetone as a solvent. In the preparations g. and r will dry acetone made by adding 30 g of calcium flour prid to 1QQ ml of a commercially available acetone, there is more than Efach leaves to stand and the desiccant is then removed by filtration,

(q) Adsorbent j Wall plaster: Solvent: Hilismediurai

Stirring conditions:

Daring and frpck.nens product:

(r) Adsprptipnsmitteli wall polymer?

Akti? Aluminumpx3rd, # g 2 | ellulpseaqetat _t 4 § dry acetone, 1Q0 iml silicone oil Clf-BS), dag % g

^ QQ ml

as in preparation (g) size Q, p = 0.8 mm.

lulyer from Amberlite Si? -p0, β g 2iellulps.eaeeta.t, 4 i ta? § @ kenes Aeetpn, IQQ ml

s paraffin dßr »» Japanese

pdag Q, p §S Laneae ent? holds,

gge Q, ^ f r- 0, | mm.

4Q9328 / Q866

τ- 18 Example 3

The adsorption capacity of the preparations (a), (b) and (e) of Example 1 and several "yergleiehsZubereitungen is tested ge ^. As a substrate, Q, Q1 follow aqueous Iiösung is used by methylene blue (molecular weight = 374)? To this solution is given by Each preparation and Vergleiehszubereitung the Iquivalent to 1 g of adsorbent, and then is stirred for "Haehdem the mixture was left for 24 hours Mplekularsiebteilehen be a the absorption of the filtrate was removed by filtration.. at the wavelength §95 Wii wjLed with The results are shown in table 1:

Table 1

| _ 1 Cujibe, = -: ! 3 "

ägiι Markenngii;
of Sakeda Öhe.mieai Industries) 0

_ Ci) Q.-

Preparation (b). 9f§iO §4

Preparation (s) 6

2 (trade

Easel Qg ₉

Compare
illGhe

§Ii I ^ the Easel Go.}

# Absorption de§ Sy [bstr§t§:

a | §s (Absorp.ticfla des ** Adsprptipnsgrad _m

x 100 Z.09828 / 086Q

- 19 Example 4

The adsorption capacity of the preparations obtained in Example 2 (g), (h), (i) and (k) and several comparator products were tested. The results are in Table 2 listed.

Table 2 Absorption* Adsorption
Degree**· ■ 0 100 0.520 89 1,310 72 0.642 87 0.635 93 2.210 56

Comparative preparation Preparation (g) Preparation (h) Preparation (i) Preparation (k) Comparative preparation Comparative preparation 4 (commercially available

Activated carbon granules, manufactured by

Institute of Industrial Technology,

Japan) 2,950 41

Comparative preparation 5 (commercially available

Granules of activated carbon, large, manufactured

from Takeda Chemical Industries) 3,550 29

* Absorption of the substrate: 5,000 ** See definition in table

Example 5

The adsorption capacity for riboflavin of the preparation (o) from Example 2, the aluminum oxide powder (comparative preparation 6) and the preparation (q) of the comparative example (comparative preparation 7) was tested. Each preparation is added to an aqueous riboflavin solution in an amount corresponding to 1 g of aluminum oxide (optical density at 450 ταμ = 0.885).

Λ09828 / 0860

-'20 -

Each mixture is allowed to stand for 24 hours, after which the adsorbent is removed by filtration. The absorption of the ultrat at "wavelength 450 mp. Is measured. The results are shown in Table 3, in which the degree of adsorption is defined as in Table 1"

Table 3
... "■ absorption adsorption

Preparation (o) O ₉ 186 79

Comparative preparation 6 0 "216 76

Comparative preparation 7 Q ₉ , 900 0

Example 6

The adsorbability of the preparation (p) from Example 2, the Amberlite = C & = 50- = powder (Comparative preparation 8) and the preparation (r) of the Comparative Example (comparative preparation 9) is tested in the "same manner as in Example 3, where Substrate an aqueous methylene blue solution (optical density at 595 ^ a - 5ο 500) is used ifird _o The results are listed in Table 4 / xf © rin the degree of adsorption in, ® is defined in the table.

Degree

Preparation (p) O ₉ 950 - 83

8 "0 ₉ 230 96

9 3.275 40

- 21 Example 7

The molecular sieve effect of preparations (a), (b) and (f) from Example 1 and of preparations (g) to (n) from Example 2 is tested. Various organic compounds with different molecular weights are used for this test. These compounds have an adsorption rate of about 100 % when treated with unmodified activated carbon or Amberlite CG-50. All molecular sieve particles are placed in a column of 1 cm diameter in an amount corresponding to 1 g of the adsorbent content. The organic compounds mentioned, which are dissolved in 10 ml of water, are passed through the column at a flow rate of 0.5 ml / min. The column is washed thoroughly with water and then subjected to elution. A fraction collector is used to collect 5 ml of eluate at a time. For organic compound A the absorption is 595 mu and for organic compounds B to L the absorption is 280 νψ. measured. The sum of the absorption values multiplied by the volume of the eluate fraction is compared with the absorption of the introduced organic compound solution to determine the degree of elution, from which the degree of adsorption is then calculated. The results are shown in Table 5.

409828 / 086G

! Table 5

Organic molecular weight preparation

"V'gyblndün ^^^ _ g desired weight tion mg / ml adsorption sgrad {#>)

nripj. lsi mi i & ± ιιιι ^ ΈπμίΠ '

Ao methylene blue ' 374 5 100 100 100 100 -

■ · '1 - - - - 100 100 100 100 100 100 100 100

798 10 100 100 100 100 - .- - - - -. -

15 - 100 80 100 64 51 97 100 100

0 ₉ 5 100 100 100 100 ' - «.- ■ -----

5 100 100 98 100 - «, -. ---.-.-

2.5 96 90 92 95. » - -, '. = · - - »~

15 - - '= - 100 1 39 6 0 32 26 44 10 ■ 62 52 72 63 - - - "».

15 = = == = 92 050 '0 0 8 17 ^

10; 20, 25 21 25 - - -. - '- - ■ -

15 «'-» 75 0 0 0 0 0 0 0

15 - - ¹ '- - 0000000 Ό

10. ogg.Q «» - ™ «=«. = »™ ==,

• 15 c =. "^ C = 0'00OO 0 0 0"

15 - - - - 0, 0-0 0 000 0

io Oo oo ------

15 » _mCT ^ 000 0 0. 0 0 0 J2

10 0 0 O'O- - ------- P ⁵

oo

Gο polymyxin 1o280 D ₀ Tneulin 5,700 Io protein = Lyso zjm HeOOO Fo OC chymotrypsin 24,500 Go semi-alkaline =
Protease 30 _o 000 H "Pepsin 35,000 Ie egg \ ^ eiß "albumin 45,000 J _e serum "albumin 67,000 K. f -aiobulin • 156,000 Ijο urease 480,000

In the following examples it is shown that the invention Molecular sieve particles are suitable for many different uses «■

Example 8

Liquid simulated Kanamycinkulturen are prepared by reacting 80 g in 160 ml Kanamy.einsulfat is a glucose broth medium containing long with 15 minutes of heating has been sterilized at 120 ⁰ G. This liquid is then passed through a column (diameter 1 ₉ 5 cm) which is filled with 2.7 g of the molecular sieve particles from Example 1 (preparation (a)), which contain activated carbon, at a flow rate of O ₅ 5 ml / minute. The column is then washed with water and then _{eluted with an O 5} In HGl-methanol solution. The active fractions are combined, and 72.8 mg of kanamycin chloride are obtained in very high purity (degree of discoloration 99 $, purity; 98 %) and high yield (91 *).

Example 9

Ia a 500 ml Sakaguehi flask are given 100 ml of a medium that contains 1 fo starch, 1 # waste molasses, 1 $ peptone and 1 $> meat extract "Each medium is ^{sterilized for 30 minutes at 120 0} C" Then each Medium with Streptomyces glizeobarohsiratufl parietus tuberacticus No. 6-130 (Deposit No. 619 at the Institute of Fermentation Research, Japan) inoculated, and the cultivation is carried out at 30 ⁰ G for 2 days, with a shaking culture device with a deflection of 7 cm and 130 shaking movements per minute is used. 4-00 ml of this liquid is transferred under aseptic conditions into a medium prepared by adding 5 ml of © ines defoaming agent (Uniol-D-2000j brand name; product of Nihon Xushi Co.) to 20 liters of a medium containing 1 $> starch , Contains 1% waste molasses, 1 pound peptone and 1 % meat extract,

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and has been produced by sterilizing this medium in a 30 l fermentation device at 120 ^° C. for 30 minutes. Cultivation is continued for 92 hours at 30 ^° C. with the supply of sterilized air in an amount of 20 l / minute and with stirring at a speed of 200 rpm, and 19 liters of a cooling liquid containing 2260 mg / ml tuberactinomycin are obtained -N contains. The solid components are now removed from this liquid. 50 ml of the clear liquid obtained are treated in a column of 1 cm diameter filled with 3 g of the active carbon-containing molecular sieve particles obtained in Example 1 (preparation (a)), after which they are washed with water and washed with 0.1N Hydrochloric acid are eluted. The eluate obtained contains tuberactinomycin-N-hydrochloride without eluting the colored substances. After this eluate is neutralized with sodium hydroxide, it is concentrated under reduced pressure to remove the sodium chloride precipitated by filtration until the concentrate is reduced to 2 ml. 14 ml of methanol are then added to the concentrate. The precipitate that forms when the mixture is left to stand overnight at 5 ° C is collected by filtration, washed with methanol and then dried under reduced pressure to give 79.7 mg of crude tuberactinomycin JT hydrochloride (yield: 67 #, purity: $ 95).

Example 10

10 mg of alkali metal phosphates (molecular weight = 100,000) are dissolved in 10 ml of a 10 ml aqueous crystal violet solution (absorption at 590 ΐημ = 5.1). The resulting solution is passed through a column 1 cm in diameter filled with 4 g of the activated carbon-containing molecular sieve particles obtained from Example 1 (preparation (a)), at a rate of 0.5 ml / minute. The degree of discoloration of the drain obtained is 99 fo. When 0.5 ml of this effluent is added to a mixture containing 0.2 ml of 0.01 mol of para-nitrophenyl phosphate, 1 ml of 0.1 mol of boric acid

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containing buffer solution and 0.3 ml of water, and to this mixture at 37 C can be 10 minutes to react for ⁰ and then 1 ml of 0.5 N sodium hydroxide is added, so to obtain a solution containing 9.7 mg (yield: 97 $) ' Alkaliphosphate se contains, as is determined by measuring the absorption at 420 τημ.

Example 11

A simulated serum kanamycin solution is prepared by dissolving 50 mg of kanamycin, 1 g of V ^ globulin, and 1 g of serum albumin in 10 ml of an Isbtonian sodium chloride solution. The solution is passed through a column 1.5 cm in diameter filled with 2.5 g of the molecular sieve particles obtained in Example 1 (preparation (c)) and containing activated carbon, at a rate of 0.5 ml /Minute. The column is then washed with water and it is eluted (5 ml per fraction) with 0.01N HCl-methanol (1: 1). Fractions 2 to 35 are combined, and 46 mg of kanamycin are obtained (yield: 92 ^c β>) .

Example 12

Methylene blue (0.2 mg) is dissolved in 20 ml of a 0.05 * mol tris buffer solution (pH 7.5), then 100 mg of protein lysozyme and 500 mg of protein albumin are dissolved in it to form a solution to manufacture. The solution is passed at a rate of 0.5 ml / minute through a column 1.5 cm in diameter filled with 2.5 g of the activated carbon-containing molecular sieve particles obtained in Example 1 (preparation (a)) to obtain a To get drain. Micrococci of the strain "Micrococcus raizodicticcus ATCC 4698" are added to the drain in order to measure the decrease in turbidity due to bacterial lysis at 540 χψ. It is found that about 90 mg of protein lysozyme is present in this liquid. The effluent is passed again at a rate of 0.5 ml / minute through a column 1.5 cm in diameter, which is filled with 10 g of the in

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Example 1 (preparation (T))) obtained containing activated carbon Molecular sieve particles is filled to obtain a drain containing only protein albumin and from which Lysozyme has been removed by adsorption. This effluent has no protein lysozyme, and the one measured at 280 mp Absorption corresponds to a protein alburain content of 4-70 mg.

Example 13

An aqueous protein test solution is prepared by dissolving 5 mg of protein albumin and 5 mg of protein lysozyme in 10 ml of water (protein albumin: optical density at 280 mu: 2.74; protein lysozyme: OD at 280 τψ: 10 .H) .. The aqueous protein test solution is passed at a rate of 0.5 ml / minute through a column of 1 cm diameter, which contains 1.67 g of the activated charcoal obtained in Example 1 (preparation (f)) Molecular sieve is filled. This column is then treated with distilled water. The effluent is collected in fractions, 5 ml per fraction. 10 fractions are collected and combined. The absorption of 1 ml of the combined fractions is measured at 280 ταμ and is 0.055e. The total absorption of the runoff is therefore 2.75 », which indicates that the runoff contains 10Q fo of the protein albumin used. The column is then _{eluted with O 9} 1N hydrochloric acid. 10 fractions of 5 ml each are collected and combined. The absorption of a 1 ml fraction of the combined liquid is measured at 280 rau and amounts to

0.211. A total absorption of 10.55 is calculated for the eluate, which indicates that the eluate contains 100% of the protein lysozyme. LysGzym to saiffleln _o

Following the procedure described above, it is possible to make the protein albumin and protein lysozyme in an extremely high yield from the aqueous egg / ice test solution to be separated and recycled.

to win. This process is also suitable for obtaining protein lysozyme and other substances from protein.

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Claims (4)

- 28 claims; ί 1 Λ Molecular sieve, characterized in that it comprises absorption ^ - ^ powder, which are dispersed in the matrix of polymeric gels which have micropores. 2. Process for the production of a molecular sieve according to Claim 1, characterized in that it comprises the following stages:! Dispersion of the adsorbent powder in a solution of polymers! Material dissolved in a solvent; Dispersing the obtained Dispersion in an auxiliary medium with a boiling point higher than that of the solvent to form fine droplets to build; and finally removing the solvent. 3. The method according to claim 2, characterized in that the solvent is essentially immiscible with water and has a lower boiling point and higher vapor pressure than water, the polymeric material being in this solvent is soluble and the auxiliary medium is an aqueous solution of a surfactant or hydrophilic Is protective colloid. 4. The method according to claim 2, characterized in that a solvent, which is substantially with liquid paraffin or silicone oil is not miscible, but is miscible with water and has a lower boiling point and has higher vapor pressure than water when mixed with water; a polymeric material that works in this solvent is soluble; and liquid paraffin or silicone oil is used as the auxiliary medium. A09828 / 086Ü